KR101367772B1 - Method for the modification of polymer surfaces, such as the hydroxylation of polymer surfaces, and products thus obtained - Google Patents
Method for the modification of polymer surfaces, such as the hydroxylation of polymer surfaces, and products thus obtained Download PDFInfo
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- KR101367772B1 KR101367772B1 KR1020087011200A KR20087011200A KR101367772B1 KR 101367772 B1 KR101367772 B1 KR 101367772B1 KR 1020087011200 A KR1020087011200 A KR 1020087011200A KR 20087011200 A KR20087011200 A KR 20087011200A KR 101367772 B1 KR101367772 B1 KR 101367772B1
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- polymer
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- hydroxylation
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- 229920000642 polymer Polymers 0.000 title claims abstract description 78
- 238000005805 hydroxylation reaction Methods 0.000 title claims abstract description 32
- 230000033444 hydroxylation Effects 0.000 title claims abstract description 31
- 238000000034 method Methods 0.000 title claims description 51
- 230000004048 modification Effects 0.000 title description 5
- 238000012986 modification Methods 0.000 title description 5
- 238000006243 chemical reaction Methods 0.000 claims abstract description 60
- 125000003118 aryl group Chemical group 0.000 claims abstract description 21
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 11
- 229920002959 polymer blend Polymers 0.000 claims abstract description 9
- 125000002252 acyl group Chemical group 0.000 claims abstract description 5
- 125000003435 aroyl group Chemical group 0.000 claims abstract description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 5
- 239000001257 hydrogen Substances 0.000 claims abstract description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract 3
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 35
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 35
- 239000004696 Poly ether ether ketone Substances 0.000 claims description 31
- 229920002530 polyetherether ketone Polymers 0.000 claims description 31
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 30
- 230000008569 process Effects 0.000 claims description 14
- -1 pyrida Genyl Chemical group 0.000 claims description 12
- 238000007306 functionalization reaction Methods 0.000 claims description 10
- 239000004734 Polyphenylene sulfide Substances 0.000 claims description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 7
- 229920001955 polyphenylene ether Polymers 0.000 claims description 7
- 229920000069 polyphenylene sulfide Polymers 0.000 claims description 7
- 239000004697 Polyetherimide Substances 0.000 claims description 5
- 229920002312 polyamide-imide Polymers 0.000 claims description 5
- 229920001601 polyetherimide Polymers 0.000 claims description 5
- 150000001408 amides Chemical class 0.000 claims description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 4
- TUJKJAMUKRIRHC-UHFFFAOYSA-N hydroxyl Chemical compound [OH] TUJKJAMUKRIRHC-UHFFFAOYSA-N 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- 229920000075 poly(4-vinylpyridine) Polymers 0.000 claims description 4
- 229920003227 poly(N-vinyl carbazole) Polymers 0.000 claims description 4
- 239000004417 polycarbonate Substances 0.000 claims description 4
- 229920000515 polycarbonate Polymers 0.000 claims description 4
- 239000004962 Polyamide-imide Substances 0.000 claims description 3
- 230000000640 hydroxylating effect Effects 0.000 claims description 3
- 150000002500 ions Chemical class 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 125000002294 quinazolinyl group Chemical group N1=C(N=CC2=CC=CC=C12)* 0.000 claims description 3
- 239000002759 woven fabric Substances 0.000 claims description 3
- 125000005428 anthryl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C(*)=C([H])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 claims description 2
- 235000010290 biphenyl Nutrition 0.000 claims description 2
- 239000004305 biphenyl Substances 0.000 claims description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 claims description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000001041 indolyl group Chemical group 0.000 claims description 2
- 125000001624 naphthyl group Chemical group 0.000 claims description 2
- 125000004934 phenanthridinyl group Chemical group C1(=CC=CC2=NC=C3C=CC=CC3=C12)* 0.000 claims description 2
- 125000004625 phenanthrolinyl group Chemical group N1=C(C=CC2=CC=C3C=CC=NC3=C12)* 0.000 claims description 2
- 125000005561 phenanthryl group Chemical group 0.000 claims description 2
- 229920000314 poly p-methyl styrene Polymers 0.000 claims description 2
- 125000001725 pyrenyl group Chemical group 0.000 claims description 2
- 125000004076 pyridyl group Chemical group 0.000 claims description 2
- 125000000714 pyrimidinyl group Chemical group 0.000 claims description 2
- 125000002943 quinolinyl group Chemical group N1=C(C=CC2=CC=CC=C12)* 0.000 claims description 2
- 125000001567 quinoxalinyl group Chemical group N1=C(C=NC2=CC=CC=C12)* 0.000 claims description 2
- 125000001544 thienyl group Chemical group 0.000 claims description 2
- 239000004695 Polyether sulfone Substances 0.000 claims 1
- 230000001747 exhibiting effect Effects 0.000 claims 1
- 229920000885 poly(2-vinylpyridine) Polymers 0.000 claims 1
- 229920006393 polyether sulfone Polymers 0.000 claims 1
- 125000003373 pyrazinyl group Chemical group 0.000 claims 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 claims 1
- 239000000243 solution Substances 0.000 description 14
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 12
- 238000004458 analytical method Methods 0.000 description 12
- 238000002042 time-of-flight secondary ion mass spectrometry Methods 0.000 description 11
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 9
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 9
- 238000011282 treatment Methods 0.000 description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 8
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 8
- 238000002329 infrared spectrum Methods 0.000 description 7
- 229920001234 Polybisphenol-A terephthalate Polymers 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000000178 monomer Substances 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- LGJCFVYMIJLQJO-UHFFFAOYSA-N 1-dodecylperoxydodecane Chemical compound CCCCCCCCCCCCOOCCCCCCCCCCCC LGJCFVYMIJLQJO-UHFFFAOYSA-N 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 229920001577 copolymer Polymers 0.000 description 5
- 239000012153 distilled water Substances 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 230000003247 decreasing effect Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229920001707 polybutylene terephthalate Polymers 0.000 description 4
- 229920000728 polyester Polymers 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 238000000527 sonication Methods 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- QAEDZJGFFMLHHQ-UHFFFAOYSA-N trifluoroacetic anhydride Chemical compound FC(F)(F)C(=O)OC(=O)C(F)(F)F QAEDZJGFFMLHHQ-UHFFFAOYSA-N 0.000 description 4
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 3
- 229920012266 Poly(ether sulfone) PES Polymers 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 150000002148 esters Chemical group 0.000 description 3
- 229920001600 hydrophobic polymer Polymers 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229920000742 Cotton Polymers 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 229920005603 alternating copolymer Polymers 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
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- 239000012634 fragment Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 150000002431 hydrogen Chemical group 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 238000002513 implantation Methods 0.000 description 2
- 239000012212 insulator Substances 0.000 description 2
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 2
- 229910000358 iron sulfate Inorganic materials 0.000 description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 2
- 125000005740 oxycarbonyl group Chemical group [*:1]OC([*:2])=O 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 229920000128 polypyrrole Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 229920000123 polythiophene Polymers 0.000 description 2
- 102000004169 proteins and genes Human genes 0.000 description 2
- 108090000623 proteins and genes Proteins 0.000 description 2
- 229920005604 random copolymer Polymers 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 125000004044 trifluoroacetyl group Chemical group FC(C(=O)*)(F)F 0.000 description 2
- 238000005583 trifluoroacetylation reaction Methods 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 238000006751 Mitsunobu reaction Methods 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004963 Torlon Substances 0.000 description 1
- 229920003997 Torlon® Polymers 0.000 description 1
- YZCKVEUIGOORGS-NJFSPNSNSA-N Tritium Chemical compound [3H] YZCKVEUIGOORGS-NJFSPNSNSA-N 0.000 description 1
- 238000006959 Williamson synthesis reaction Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001335 aliphatic alkanes Chemical group 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 238000010640 amide synthesis reaction Methods 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 229940088710 antibiotic agent Drugs 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical group C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
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- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 229910001447 ferric ion Inorganic materials 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000013505 freshwater Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
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- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000011221 initial treatment Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- GSRMOLMSZKTISY-UHFFFAOYSA-N iron(2+);iron(3+) Chemical compound [Fe+2].[Fe+3] GSRMOLMSZKTISY-UHFFFAOYSA-N 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 150000002576 ketones Chemical group 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
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- 229920001296 polysiloxane Polymers 0.000 description 1
- 238000004313 potentiometry Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 150000003138 primary alcohols Chemical class 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 125000002098 pyridazinyl group Chemical group 0.000 description 1
- 125000000168 pyrrolyl group Chemical group 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000012047 saturated solution Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 229920000638 styrene acrylonitrile Polymers 0.000 description 1
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- 238000002054 transplantation Methods 0.000 description 1
- 125000000876 trifluoromethoxy group Chemical group FC(F)(F)O* 0.000 description 1
- 238000006692 trifluoromethylation reaction Methods 0.000 description 1
- 229920000785 ultra high molecular weight polyethylene Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/12—Chemical modification
- C08J7/16—Chemical modification with polymerisable compounds
- C08J7/18—Chemical modification with polymerisable compounds using wave energy or particle radiation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/12—Chemical modification
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Toxicology (AREA)
- Treatments Of Macromolecular Shaped Articles (AREA)
Abstract
본 발명은 RO·라디칼(R은 수소, 2 내지 15 탄소를 갖는 알킬기, 아실기 -COR'(R'는 2 내지 15 탄소를 갖는 알킬기), 또는 아로일기 -COAr(Ar은 6 내지 15 탄소를 갖는 방향족기)이다)을 폴리머 또는 폴리머 혼합물 표면의 하이드록실화, 알콕시화, 또는 옥시카보닐화에 사용하는 방법에 관한 것으로서, 상기 폴리머는 모노머 단위로 구성되고, 이들 중 50% 이상이 방향족 단위이며, 상기 RO·라디칼은 전기화학적 또는 광화학적 수단에 의해 생성된다.The present invention relates to RO radicals (R is hydrogen, an alkyl group having 2 to 15 carbons, an acyl group -COR '(R' is an alkyl group having 2 to 15 carbons), or an aroyl group -COAr (Ar is 6 to 15 carbons). To a hydroxylation, alkoxylation, or oxycarbonylation of a polymer or polymer mixture surface, wherein the polymer is composed of monomeric units, at least 50% of which are aromatic units. The RO radicals are produced by electrochemical or photochemical means.
폴리머의 하이드록실화, 펜톤 반응, RO·라디칼Hydroxylation of polymers, Fenton reaction, RO radical
Description
본 발명은 폴리머 표면 개질 방법, 특히 폴리머 표면의 하이드록실화 방법 및 개질된 표면에 관한 것이다.The present invention relates to methods of polymer surface modification, in particular to the hydroxylation of polymer surfaces and to modified surfaces.
전기이식(Electrografting)은 전기전도성 및 반전도성 표면이 기능화되도록 한다. 전기이식의 주된 이점 중 하나는 계면 결합의 형성 및 표면상의 필름 성장 양자를 허용하는 에너지이다: 따라서 그 고유의 기능화를 생성하는 것은 표면 그 자체이다. 이러한 성질은 예를 들면 전기이식된 층이 수행되는 표면 토폴로지(surface topology)를 매우 정확하게, 거의 나노미터 스케일로 채운다는 결과를 낳는다. 거시적 스케일로 보면, 전기이식은 임의 형태의 복합성을 갖는 부분들 위에 매우 고른 질적 완성도로 코팅되게 한다: 전기이식 용액에 의하여 습윤된 표면은 어디에나 전기이식 필름이 형성된다.Electrografting allows the electroconductive and semiconductive surfaces to be functionalized. One of the main advantages of electrotransplantation is the energy that allows both the formation of interfacial bonds and film growth on the surface: thus it is the surface itself that creates its own functionalization. This property results in, for example, filling the surface topology on which the electrografted layer is carried out very accurately, almost on the nanometer scale. On a macro scale, electrotransplantation allows coating of evenly shaped parts with very even qualitative completeness: electrowetting films are formed everywhere on the surface wetted by the electrotransfer solution.
절연 표면의 경우 전기수단에 의하여 절연체를 직접 활성화하는 것은 그 본 성상 불가능하기 때문에, 최소한 통상의 형태로서는 절연 표면상에 전기이식을 수행하는 것은 명백히 불가능하다.Since the direct activation of the insulator by electrical means in the case of an insulating surface is not inherently possible, it is obviously impossible to carry out electrotransplantation on the insulating surface, at least in its usual form.
어떠한 형태의 표면에서도 유사한 질의 기능화를 제안하기 위해서는, 분자 전구체 또는 표면 활성화 기술에 의하여 전기이식에 필요한 필수적인 요소를 유지하게 하는 특이성을 검색함으로써, 절연체에 대한 이식 방법을 개발하는 것이 필요하다: 계면 결합(공유 또는 비공유), 일치성, 균일성. To suggest similar quality functionalization on any type of surface, it is necessary to develop implantation methods for insulators by searching for specificities that enable molecular precursors or surface activation techniques to maintain the essential elements necessary for electrotransplantation: interfacial bonding (Shared or non-shared), consistency, uniformity.
폴리머 표면을 기능화하여 친수성, 소수성, 단백질 또는 다른 생물학적 분자의 흡착 또는 비-흡착, 어떠한 형태의 유기 또는 무기 물질의 결합, 접착성, 보다 일반적이고 바람직한 원하는 적용을 위한 특정 성질을 부여하는 것은 흥미로우며, 이는 고려되는 대상의 표면에 의해 제공되는 기능의 개질로 지칭될 수 있다. 이는 직접, 또는 표면을 더욱 활성화하는 초기 처리 이후, 후-기능화에 의해 실현될 수 있다. It is interesting to functionalize the polymer surface to impart specific properties for the adsorption or non-adsorption of hydrophilicity, hydrophobicity, proteins or other biological molecules, binding of any form of organic or inorganic material, adhesion, and more general and desirable desired applications. This may be referred to as a modification of the function provided by the surface of the object under consideration. This can be realized either directly or after initial treatment to further activate the surface, by post-functionalization.
본 발명의 목적은 폴리머 표면에서 개질된 표면을 제조하는 방법, 특히 OH·또는 OR·라디칼을 사용하여 폴리머 표면에서 개질된 표면을 제조하는 방법을 제공하는 것이다.It is an object of the present invention to provide a method for producing a modified surface on a polymer surface, in particular a method for producing a modified surface on a polymer surface using OH or OR radicals.
본 발명의 다른 목적은 개질된 폴리머 표면, 특히 후속되는 기능화 반응에서 사용될 수 있는 친수성으로 제조되는 개질된 폴리머 표면을 제공하는 것이다.Another object of the present invention is to provide a modified polymer surface, in particular a modified polymer surface that is made hydrophilic that can be used in subsequent functionalization reactions.
본 발명은 RO·라디칼(R은 수소, 2 내지 15 탄소를 갖는 알킬기, 아실기 -COR'(R'는 2 내지 15 탄소를 갖는 알킬기), 또는 아로일기 -COAr(Ar은 6 내지 15 탄소를 갖는 방향족기)이다)을 폴리머 또는 폴리머 혼합물 표면, 특히 소수성인 폴리머 또는 폴리머 혼합물 표면의 하이드록실화, 알콕시화, 또는 옥시카보닐화에 사용하는 방법에 관한 것으로서, 상기 폴리머는 50% 이상이 방향족 단위인 모노머 단위들로 구성되고, 상기 RO·라디칼은 전기화학적 또는 광화학적 수단에 의해 생성된다.The present invention relates to RO radicals (R is hydrogen, an alkyl group having 2 to 15 carbons, an acyl group -COR '(R' is an alkyl group having 2 to 15 carbons), or an aroyl group -COAr (Ar is 6 to 15 carbons). ) To a hydroxylation, alkoxylation, or oxycarbonylation of a polymer or polymer mixture surface, especially a hydrophobic polymer or polymer mixture surface, wherein at least 50% of the polymers are aromatic units. Consists of phosphorus monomer units, the RO radicals are produced by electrochemical or photochemical means.
본 발명은 또한 HO·하이드록실 라디칼을 소수성 폴리머 표면의 하이드록실화에 사용하는 방법에 관한 것이며, 상기 폴리머는 50% 이상이 방향족 단위인 모노머 단위들로 구성된다.The invention also relates to the use of HO-hydroxyl radicals for the hydroxylation of hydrophobic polymer surfaces, wherein the polymer consists of monomeric units of at least 50% being aromatic units.
본 발명에서 "표면 하이드록실화"는 상기 표면에 하이드록실기(-OH)의 결합을 의미한다."Surface hydroxylation" in the present invention means a bond of a hydroxyl group (-OH) to the surface.
본 발명에서 "표면 알콕시화"는 상기 표면에 알콕시기(-OR)의 결합을 의미하며, R은 상기 정의된 알킬기이다.In the present invention, "surface alkoxylation" means a bond of an alkoxy group (-OR) to the surface, and R is an alkyl group as defined above.
본 발명에서 "표면 옥시카보닐화"는 상기 표면에 옥시카보닐기(-OCOR' 또는 -OCOAr, R' 및 Ar은 상기 정의된 바와 같다)의 결합을 의미한다."Surface oxycarbonylation" in the present invention means the bonding of an oxycarbonyl group (-OCOR 'or -OCOAr, R' and Ar are as defined above) to the surface.
본 발명에서 "폴리머 혼합물"은 두개 이상의 폴리머를 혼합함으로써 수득되는 물질을 의미한다. 예를 들면, 폴리머 아크릴로니트릴-부타디엔-스티렌은 이식 엘라스토머 상(부타디엔)을 스티렌상: 스티렌-아크릴로니트릴 코폴리머내에 분산시켜 수득된 물질이다.By "polymer mixture" is meant herein a material obtained by mixing two or more polymers. For example, polymer acrylonitrile-butadiene-styrene is a material obtained by dispersing the implanted elastomer phase (butadiene) in the styrene phase: styrene-acrylonitrile copolymer.
본 발명에서 "모노머 단위들"은 폴리머내 반복 단위들을 의미한다. By "monomer units" is meant repeat units in the polymer.
본 발명에서 "방향족 단위들"은 방향족 고리, 즉 전체 고리내 데로컬라이즈드된 4n+2 전자를 포함하는 고리를 포함하는 단위들을 의미한다. "Aromatic units" in the present invention means units comprising an aromatic ring, ie a ring comprising 4n + 2 electrons delocalized in the entire ring.
본 발명은 또한 펜톤 반응을 폴리머 또는 폴리머 혼합물의 하이드록실화, 알콕시화 또는 옥시카보닐화에 사용하는 방법에 관한 것이며, 상기 폴리머는 50% 이상이 방향족 단위인 모노머 단위들로 구성되며, 펜톤 반응은 전기화학적 또는 광화학적 수단에 의해 수행된다.The invention also relates to a process for using the Fenton reaction for hydroxylation, alkoxylation or oxycarbonylation of a polymer or polymer mixture, wherein the polymer consists of monomeric units of at least 50% aromatic units, It is carried out by electrochemical or photochemical means.
본 발명에서 "펜톤 반응"은 과산화수소(hydeogen peroxide)와 철(II)의 반응에 의하여 하이드록실 라디칼을 생성하는 반응을 의미한다.In the present invention, the "Fenton reaction" refers to a reaction for generating hydroxyl radicals by the reaction of hydrogen peroxide and iron (II).
상기 반응은 아래의 반응도로 나타낼 수 있다.The reaction can be represented by the following reaction diagram.
상기 반응은 특히 하기 문헌에 개시되어 있다: Fenton, H., J., H. J. Chem . Soc. 1894, 65, 899 ; Haber, F.; Weiss, J. Proc . Roy . Soc . A. 1934, 134, 332 ; Barb.; W.G.; Baxendale, J., H.; George, P.; Hargrave, K. R. Nature 1949, 163, 692 ; Walling, C.; Weil, T. Int . J. Chem . Kinet. 1974, 6, 507 ; Gallard, H.; DeLaat, J.; Legube, B. Wat . Res . 1999, 33, 2929.The reaction is disclosed in particular in the following documents: Fenton, H., J., H. J. Chem . Soc . 1894 , 65 , 899; Haber, F .; Weiss, J. Proc . Roy . Soc . A. 1934 , 134 , 332; Barb .; WG; Baxendale, J., H .; George, P .; Hargrave, KR Nature 1949 , 163 , 692; Walling, C .; Weil, T. Int . J. Chem . Kinet . 1974 , 6 , 507; Gallard, H .; DeLaat, J .; Legube, B. Wat . Res . 1999 , 33 , 2929.
상기 반응은 본 발명의 범위내에서 과산화수소를 퍼옥사이드 ROOR(R은 상기 정의된 바와 같다)로 대체하여 응용할 수 있다.The reaction can be applied by replacing hydrogen peroxide with peroxide ROOR (R is as defined above) within the scope of the present invention.
방향족 단위, 특히 PEEK를 갖는 다양한 폴리머는 생의학적 응용에 사용된다. 이러한 응용을 위하여 사용자는 폴리머의 기계적 성질을 유지면서, 표면은 친수성으로 만들 수 있기를 요망한다. 또한 표면 하이드록실화는 후에 후-기능화, 즉 표면에 특정 성질을 갖는 새로운 기능기를 결합하는 반응을 수행할 수 있도록 한다.Various polymers having aromatic units, in particular PEEK, are used in biomedical applications. For this application the user wants to be able to make the surface hydrophilic while maintaining the polymer's mechanical properties. Surface hydroxylation also makes it possible to carry out post-functionalization, ie reactions that bind new functional groups with specific properties to the surface.
특히, PEEK 하이드록실화에 관하여, 상기 반응은 지금까지 케톤 기능기의 환원(Noiset, O.; Schneider, Y.-J.; Marchand-Brynaert, J. J. Biomat . Sci ., Polymer Ed. 2000, 11, 767 ; Henneuse-Boxus, C.; De Ro, A.; Bertrand, P.; Marchand-Brynaert, J. Polymer 2000, 41, 2339 ; Henneuse-Boxus, C.; Poleunis, C.; De Ro, A.; Adriaensen, Y.; Bertrand, P.; Marchand-Brynaert, J. Surface and Interface Analysis 1999, 27, 142 ; Noiset, O.; Schneider, Y-J; Marchand-Brynaert, J. J. Pol. Sci., Part A: Polymer Chemistry 1997, 35, 3779), 에스테르 기능기의 가수분해에 의한 PET(Mougenot, P.; Koch, M.; Dupont, I.; Schneider, Y.-J.; Marchand-Brynaert, J. J. Colloid and Interface Sci. 1996, 177, 162), 플라즈마(Cheng, T.-S.; Lin, H.-T.; Chuang, M.-J. Materials Letters 2004, 58, 650) (상기 저자들은 하나의 친수성 면 및 다른 하나의 소수성 면을 제조하는데 성공하였다)에 의해 수행되어 왔다.In particular, with respect to PEEK hydroxylation, the reaction has so far been reduced by ketone functional groups (Noiset, O .; Schneider, Y.-J .; Marchand-Brynaert, J. J. Biomat . Sci ., Polymer Ed . 2000 , 11 , 767; Henneuse-Boxus, C .; De Ro, A .; Bertrand, P .; Marchand-Brynaert, J. Polymer 2000 , 41 , 2339; Henneuse-Boxus, C .; Poleunis, C .; De Ro , A .; Adriaensen, Y .; Bertrand, P .; Marchand-Brynaert, J. Surface and Interface Analysis 1999 , 27, 142; Noiset, O .; Schneider, YJ; Marchand-Brynaert, JJ Pol. Sci., Part A: Polymer Chemistry 1997 , 35, 3779), PET by hydrolysis of ester functional groups (Mougenot, P .; Koch, M .; Dupont, I .; Schneider, Y.-J .; Marchand- Brynaert, J. J. Colloid and Interface Sci . 1996 , 177, 162), plasma (Cheng, T.-S .; Lin, H.-T .; Chuang, M.-J. Materials Letters 2004 , 58 , 650 (The authors have succeeded in producing one hydrophilic cotton and the other hydrophobic cotton).
펜톤반응, 전기펜톤반응, 광펜톤반응을 이용하는 것은 특히 유리한데, 이러한 반응들은 폴리머의 화학적 구조에 상관없이 폴리머에 적용가능하기 때문이다: 따라서 반응은 폴리머의 화학적 구조에 비-특이적이다.It is particularly advantageous to use the Fenton, Electro-Fenton, or Photo-Fenton reactions because these reactions are applicable to polymers regardless of their chemical structure: the reaction is therefore non-specific to the chemical structure of the polymer.
본 발명의 일 실시형태에 따르면, 본 발명은 펜톤 반응이 전기화학적 수단, 즉 전기펜톤 반응을 이용하여 실현되는 것을 특징으로 하는 상기 정의된 바와 같은 방법에 관한 것이다.According to one embodiment of the invention, the invention relates to a method as defined above, wherein the Fenton reaction is realized using electrochemical means, i.
전기펜톤 반응(Tomat, R.; Vecchi, A. J. Appl . Electrochem . 1971, 1, 185; Oturan, M. A.; Pinson, J. New J. Chem 1992, 16, 705 ; Fang, X.; Pam, X.; Rahman, A. P. Chem . Eur . J.. 1995, 1, 423 ; Gallard, H.; DeLaat, J. Chemosphere 2001, 42, 405 ; Matsue.T., Fujihira, M.; Osa, T. J. Electrochem.Soc. 1981, 128, 2565 ; Fleszar, B.; Sobkoviak, A. Electrochim . Act. 1983, 28, 1315 ; Tzedakis, T.; Savall, A.;Clifton, M., J. J. Appl . Electrochem. 1989, 19, 911 ; Oturan, M. A.; Oturan, N.; Lahitte, C.; Trevin, S. J. Electranal . Chem. 2001, 507, 96 ; Brillas, E.; Casado, J. Chemosphere 2002, 47, 241)은 펜톤 반응의 일 변형이며, 산소가 환원되어 과산화수소를 생성하는 동시에 캐소드에서 Fe2 +가 끊임없이 재생성되는 촉매 반응으로 구성되어 있다. Electrophentone reactions (Tomat, R .; Vecchi, A. J. Appl . Electrochem . 1971 , 1 , 185; Oturan, MA; Pinson, J. New J. Chem 1992 , 16 , 705; Fang, X .; Pam, X .; Rahman, A. P. Chem . Eur . J .. 1995 , 1, 423; Gallard, H .; DeLaat, J. Chemosphere 2001 , 42 , 405; Matsue. T., Fujihira, M .; Osa, T. J. Electrochem . Soc. 1981 , 128 , 2565; Fleszar, B .; Sobkoviak, A. Electrochim . Act. 1983 , 28 , 1315; Tzedakis, T .; Savall, A .; Clifton, M., J. J. Appl . Electrochem . 1989 , 19 , 911; Oturan, MA; Oturan, N .; Lahitte, C .; Trevin, S. J. Electranal . Chem . 2001 , 507 , 96; Brillas, E .; Casado, J . the modification of Chemosphere 2002, 47, 241) is the Fenton reaction, oxygen is reduced at the cathode at the same time is configured to generate the hydrogen peroxide to the catalyst reaction is Fe + 2 are constantly regenerated.
펜톤 반응이 과산화수소 및 Fe2 +가 혼합하여 "블라스트"에 의하여 하이드록실 라디칼을 생성하는 반면(즉 하이드록실 라디칼의 신속한 제조), 전기펜톤 반응은 철(II)의 철(III)으로의 감축을 허용하는 전위가 유지되는 한 상기 라디칼을 계속하여 생성할 수 있다. 또한 상기 반응은 최종적으로 CO2와 H20로 변환되는 독성 유출물을 수 시간내에 완전히 분해하는데 사용된다. On the other hand the Fenton reaction of hydrogen peroxide and Fe 2 + is a mixture of generating the hydroxyl radicals by the "blast" (i.e. hydroxyl rapid production of hydroxyl radicals), the electric Fenton reaction is the reduction of the iron (III) iron (II) The radicals can continue to be produced as long as the permissible potential is maintained. The reaction is also used to completely detoxify the toxic effluent that is finally converted to CO 2 and H 2 O in a few hours.
상기 촉매 사이클을 하기에 도시한다:The catalyst cycle is shown below:
본 발명의 다른 실시형태에 따르면, 본 발명은 펜톤 반응이 광화학적 수단에 의하여 실현되는, 즉 광펜톤 반응을 이용하여 실현되는 것을 특징으로 하는 상기 정의된 방법에 관한 것이다.According to another embodiment of the present invention, the present invention relates to a method as defined above, wherein the Fenton reaction is realized by photochemical means, i.e., using a photofenton reaction.
광펜톤반응(Brillas, E.; Sauleda, R.; Casado, J. J. Electrochem . Soc . 1998, 145, 759)은 펜톤 반응의 변형이며, 하기 기전을 갖는다:Photofenton reactions (Brillas, E .; Sauleda, R .; Casado, J. J. Electrochem . Soc . 1998 , 145 , 759) are variations of the Fenton reaction and have the following mechanism:
전기펜톤반응과 마찬가지로, 본 반응은 과산화수소가 존재하는 한, 하이드록실 라디칼을 계속하여 생성할 수 있다.Like the electrofenton reaction, the reaction can continue to produce hydroxyl radicals, as long as hydrogen peroxide is present.
본 발명은 또한 하이드록실화, 알콕시화 또는 옥시카보닐화된 표면을 수득하기 위한 폴리머 또는 폴리머 혼합물 표면을 하이드록실화, 알콕시화, 또는 옥시카보닐화하는 방법에 관한 것으로서, 상기 폴리머는 모노머 단위로 구성되고, 이들 중 50%이상이 방향족 단위이며, 상기 방법은 RO·라디칼(R은 수소, 2 내지 15 탄소를 갖는 알킬기, 아실기 -COR'(R'는 2 내지 15 탄소를 갖는 알킬기, 특히 부틸 또는 라우릴기), 또는 아로일기 -COAr(Ar은 6 내지 15 탄소를 갖는 방향족기, 특히 페닐기)이다)을 표면과 반응시키는 단계로 이루어지며, RO·라디칼은 전기화학적 또는 광화학적 수단에 의해 생성되는 것을 특징으로 한다.The invention also relates to a process for hydroxylating, alkoxylating, or oxycarbonylating a polymer or polymer mixture surface to obtain a hydroxylated, alkoxylated or oxycarbonylated surface, the polymer comprising monomer units. Wherein at least 50% of these are aromatic units, and the process comprises RO radicals (R is hydrogen, an alkyl group having from 2 to 15 carbons, an acyl group -COR '(R' is an alkyl group having from 2 to 15 carbons, in particular butyl Or a lauryl group), or an aroyl group —COAr (Ar is an aromatic group having 6 to 15 carbons, in particular a phenyl group), with the surface, and the RO radical is formed by electrochemical or photochemical means. It is characterized in that the generated.
본 발명에서 "하이드록실화된 표면"은 하이드록실기(-OH)를 함유하는 표면을 의미한다.By "hydroxylated surface" is meant herein a surface containing hydroxyl groups (-OH).
본 발명에서 "알콕시화된 표면"은 알콕시기(-OR)를 함유하는 표면을 의미하며, R은 상기 정의된 바와 같은 알킬기이다.By "alkoxylated surface" is meant herein a surface containing an alkoxy group (-OR), where R is an alkyl group as defined above.
본 발명에서 "옥시카보닐화된 표면"은 옥시카보닐기(-OCOR' 또는 -OCOAr, R' 및 Ar은 상기 정의된 바와 같다)를 함유하는 표면을 의미한다.By "oxycarbonylated surface" is meant herein a surface containing an oxycarbonyl group (-OCOR 'or -OCOAr, R' and Ar are as defined above).
본 발명의 일 실시형태에 따라 수득된 옥시카보닐화 표면은 -COR' 또는 -COAr기(R' 및 Ar은 상기 정의된 바와 같다)를 함유한다.The oxycarbonylated surface obtained according to one embodiment of the present invention contains a -COR 'or -COAr group (R' and Ar are as defined above).
RO·라디칼은 철(II)에 의해 촉매되는 RO-OR 퍼옥사이드의 분해에 의해 수득된다.RO radicals are obtained by decomposition of RO-OR peroxides catalyzed by iron (II).
HO·라디칼은 철(II)에 의해 촉매되는 과산화수소 H2O2의 분해에 의해 수득된다.HO radicals are obtained by decomposition of hydrogen peroxide H 2 O 2 catalyzed by iron (II).
본 발명에 따른 바람직한 하이드록실화 방법은 표면을 HO·하이드록실라디칼과 반응시키는 단계를 갖는 것을 특징으로 한다.Preferred hydroxylation processes according to the invention are characterized by the step of reacting the surface with HO hydroxyl radicals.
본 발명은 또한 폴리머 표면 특히 소수성인 폴리머 표면을 하이드록실화하여 하이드록실화된 표면을 얻는 방법에 관한 것으로, 상기 폴리머는 50% 이상이 방향족 단위인 모노머 단위들로 구성되며, 상기 방향족 단위는 특히 페닐(phenyl), 안트릴(anthryl), 나프틸(naphthyl), 바이페닐(biphenyl), 페난트릴(phenanthryl), 피레닐(pyrenyl), 피리딜(pyridyl), 피리미딜(pyrimidyl), 피라지닐(pyrazinyl), 피리다지닐(pyridazinyl), 퀴녹사릴(quinoxalyl), 퀴나졸일(quinazolyl), 퀴노리닐(quinolinyl), 티오페닐(thiophenyl), 피롤일(pyrrolyl), 페난트로리닐(phenathrolinyl), 페난트리디닐(phenanthridinyl), 인돌일(indolyl) 및 카르바졸일(carbazolyl)로 이루어지는 방향족 기에서 선택되며, 상기 방법은 전기화학적 또는 광화학적 수단에 의해 펜톤 반응(전기펜톤 또는 광펜톤 반응)에 의해 얻어진 HO·하이드록실라디칼을 표면과 반응시키는 것을 특징으로 한다.The present invention also relates to a method of hydroxylating a polymer surface, in particular a hydrophobic polymer surface, to obtain a hydroxylated surface, wherein the polymer consists of monomeric units of at least 50% of aromatic units, the aromatic unit being particularly Phenyl, anthryl, naphthyl, biphenyl, phenanthryl, pyrenyl, pyridyl, pyrimidyl, pyrazinyl pyrazinyl, pyridazinyl, quinoxalyl, quinazolyl, quinazolyl, quinolinyl, thiophenyl, pyrrolyl, phenanthrolinyl, It is selected from aromatic groups consisting of phenanthridinyl, indolyl and carbazolyl, which method is carried out by a fenton reaction (electrophentone or photophentone reaction) by electrochemical or photochemical means. Obtained HO hydroxyl radicals It characterized in that that surface reaction.
상기 모노머 단위들은 하기식의 단위들에서 선택된다:The monomer units are selected from units of the formula:
폴리카보네이트(PC) 폴리페닐렌설파이드(PPS) 폴리페닐렌에테르(PPE)Polycarbonate (PC) Polyphenylene sulfide (PPS) Polyphenylene ether (PPE)
폴리에테르에테르케톤(PEEK) 폴리에틸렌테레프탈레이트(PET)Polyether ether ketone (PEEK) polyethylene terephthalate (PET)
폴리부틸렌테레프탈레이트(PBTP) 폴리에테르설폰(PES)Polybutylene Terephthalate (PBTP) Polyethersulfone (PES)
방향족 폴리아미드(110) 폴리비스페놀 A 테레프탈레이트(PAR)Aromatic Polyamide (110) Polybisphenol A Terephthalate (PAR)
폴리에테르이미드 Polyetherimide
폴리아미드-이미드(PAI) 피로멜리타이드 캅톤Polyamide-imide (PAI) pyromellitide captone
폴리스티렌 폴리4-메틸스티렌 폴리4-비닐피리딘 폴리2-비닐피리딘 
폴리비닐카바졸 폴리피롤 폴리티오펜 Polyvinylcarbazole polypyrrole polythiophene
바람직하게 본 발명에 관련된 폴리머는 폴리실록산 폴리머와 상이하다.Preferably the polymers involved in the present invention are different from the polysiloxane polymers.
본 발명은 HO·하이드록실 라디칼이 과산화수소 및 3가철(Fe3 +) 또는 2가철(Fe2+)이온을 혼합하여 수득되는 것을 특징으로 하는 상기 정의된 방법에 관한 것이다.The present invention relates to the above defined method, characterized in that HO · The hydroxyl radicals are obtained by mixing hydrogen peroxide and 3 gacheol (Fe + 3) or 2 gacheol (Fe 2+) ions.
본 발명의 바람직한 일 실시형태에 따르면, 본 발명의 방법은 HO·하이드록실 라디칼이 전기펜톤 반응에 의해 수득되는 것을 특징으로 한다.According to one preferred embodiment of the present invention, the process of the present invention is characterized in that the HO hydroxyl radical is obtained by an electrophentone reaction.
본 발명의 일 실시형태에 따르면, 본 발명의 전기펜톤 반응의 이용을 포함하는 방법은 과산화수소가 산성 매질내에서 산소의 전기화학적 환원에 의해 직접적으로 수득되는 것과 HO·하이드록실 라디칼이 2가철이온과 과산화수소의 반응에서 수득되는 것을 특징으로 한다.According to one embodiment of the present invention, a process comprising the use of the electrofenton reaction of the present invention is characterized in that hydrogen peroxide is obtained directly by electrochemical reduction of oxygen in an acidic medium and HO-hydroxyl radicals with ferric ions. It is characterized in that it is obtained in the reaction of hydrogen peroxide.
본 발명에서 "산소의 전기화학적 환원"은 산소에 두개의 전자와 두개의 프로톤이 이동되어 과산화수소를 생성하는 것을 의미한다.In the present invention, "electrochemical reduction of oxygen" means that two electrons and two protons are moved to oxygen to generate hydrogen peroxide.
"산성 매질"은 pH가 7 이하, 특히 2 내지 4, 더욱 정확하게는 3인 매질을 의미한다.By "acidic medium" is meant a medium having a pH of 7 or less, in particular 2 to 4, more precisely 3.
본 발명은 또한 HO·하이드록실 라디칼이 광펜톤 반응에 의해 수득되는 것을 특징으로 하는 상기 정의된 방법에 관한 것이다.The invention also relates to the process as defined above, wherein the HO hydroxyl radical is obtained by a photophentone reaction.
광펜톤 반응의 이용에 관한 바람직한 일 실시형태에 따르면, 본 발명의 방법은 과산화수소가 폴리머 표면에 추가되고, 과산화수소 및 2가철염, 특히 염화철 또는 황산철을 포함하는 수성 용액과 상기 표면을 접촉하고, 상기 표면 및 상기 용액의 조사에 의해 HO·하이드록실 라디칼이 수득되는 것을 특징으로 한다.According to one preferred embodiment of the use of the photofenton reaction, the process of the present invention comprises contacting the surface with an aqueous solution comprising hydrogen peroxide added to the polymer surface and comprising hydrogen peroxide and a ferric salt, in particular iron chloride or iron sulfate, The HO and hydroxyl radicals are obtained by irradiation of the surface and the solution.
상기에서 "수성 용액과 상기 표면을 접촉시킨다"는 것은 상기 표면을 상기 용액에 담그거나, 또는 상기 표면상에 상기 용액의 일정 부피, 예를 들면 한 방울을 붓는 것을 의미한다.By "contacting the surface with an aqueous solution" is meant to immerse the surface in the solution or to pour a volume, for example a drop, of the solution onto the surface.
"상기 표면 및 상기 용액의 조사"는 상기 용액 및 표면에 적절한 파장, 특히 자외선 영역의 파장, 즉 400nm 이하의 파장을 방출하는 램프로 조사하는 것을 의미한다.By "irradiation of said surface and said solution" is meant to irradiate the solution and the surface with a lamp which emits an appropriate wavelength, in particular a wavelength in the ultraviolet region, i.
본 발명의 다른 바람직한 실시형태에 따르면, 본 발명은 과산화수소 및 2가철염, 특히 염화철 또는 황산철을 포함하는 수성용액에 폴리머를 담그고, 상기 용약 및 폴리머에 UV 램프를 조사하는 것을 특징으로 하는 상기 정의된 방법에 관한 것이다.According to another preferred embodiment of the present invention, the present invention is the above definition, wherein the polymer is immersed in an aqueous solution containing hydrogen peroxide and ferric salts, in particular iron chloride or iron sulfate, and the UV lamp is irradiated to the solution and the polymer. It is about how.
본 발명은 또한 폴리머가 약 500 내지 5백만 달톤의 분자량을 갖는 모노머 단위들을 함유하는 것을 특징으로 하는 상기 정의된 방법에 관한 것이다.The invention also relates to the process as defined above, wherein the polymer contains monomer units having a molecular weight of about 500 to 5 million daltons.
분자량 500 달톤은 폴리머 분자량의 하한에 해당하며, 분자량 5백만 달톤은 UHMW(초고분자량) 폴리에틸렌의 분자량에 해당한다.The molecular weight of 500 Daltons corresponds to the lower limit of the polymer molecular weight and the 5 million Daltons corresponds to the molecular weight of UHMW (ultra high molecular weight) polyethylene.
본 발명은 또한 폴리머가 하기에서 선택되는 것을 특징으로 하는 상기 정의된 방법에 관한 것이다: 폴리카보네이트(PC), 폴리페닐렌설파이드(PPS), 폴리페닐렌에테르(PPE), 폴리에테르에테르케톤(PEEK), 폴리에틸렌테레프탈레이트(PET), 폴리에테르설폰(PES), 폴리방향족아미드(PPA), 폴리비스페놀 A 테레프탈레이트(PAR), 폴리에테르이미드(PEI), 폴리아미드-이미드(PAI, Torlon®), 폴리피로멜리타이드(캅톤®, 스티렌), 폴리(4-메틸스티렌), 폴리(4-비닐피리딘)(4VP) 또는 폴리2-비닐피리딘(2VP) 및 폴리비닐카바졸.The present invention also relates to the process as defined above, wherein the polymer is selected from: polycarbonate (PC), polyphenylene sulfide (PPS), polyphenylene ether (PPE), polyether ether ketone (PEEK) ), Polyethylene terephthalate (PET), polyethersulfone (PES), polyaromatic amide (PPA), polybisphenol A terephthalate (PAR), polyetherimide (PEI), polyamide-imide (PAI, Torlon ® ) , Polypyromellitide (Capton ® , styrene), poly (4-methylstyrene), poly (4-vinylpyridine) (4VP) or poly2-vinylpyridine (2VP) and polyvinylcarbazole.
각 폴리머들의 식을 하기에 도시한다:The formula of each polymer is shown below:
폴리카보네이트(PC) 폴리페닐렌설파이드(PPS) 폴리페닐렌에테르(PPE)Polycarbonate (PC) Polyphenylene sulfide (PPS) Polyphenylene ether (PPE)
폴리에테르에테르케톤(PEEK) 폴리에틸렌테레프탈레이트(PET)Polyether ether ketone (PEEK) polyethylene terephthalate (PET)
폴리부틸렌테르프탈레이트(PBTP) 폴리에테르설폰(PES)Polybutylene Terephthalate (PBTP) Polyethersulfone (PES)
폴리방향족 아미드(110) 폴리비스페놀 A 테레프탈레이트(PAR)Polyaromatic amide (110) polybisphenol A terephthalate (PAR)
폴리아미드-이미드(PAI) 피로멜리타이드 캅톤Polyamide-imide (PAI) pyromellitide captone
폴리스티렌 폴리4-메틸스티렌 폴리4-비닐피리딘 폴리2-비닐피리딘 
폴리비닐카바졸 폴리피롤 폴리티오펜 Polyvinylcarbazole polypyrrole polythiophene
본 발명은 또한 폴리머가 하나 이상의 방향족 단위, 특히 펜단트 아릴기(pendant aryl group)와 하나 이상의 알칸 단위를 갖는 모노머 단위로 구성되고, 상기 폴리머가 랜덤 코폴리머, 교대 코폴리머 및 블록 코폴리머(디블록, 트리블록, 멀티블록 또는 방사상)에서 선택되는 것을 특징으로 하는 상기 정의된 방법에 관한 것이다.The present invention also relates to polymers comprising monomer units having at least one aromatic unit, in particular pendant aryl groups and at least one alkane unit, wherein the polymer is a random copolymer, an alternating copolymer and a block copolymer (diblock , Treeblock, multiblock or radial).
교대 코폴리머는 하기 형태의 폴리머이다: -ABABABAB-.The alternating copolymers are polymers of the form: -ABABABAB-.
블록 또는 순차 코폴리머는 하기 형태의 폴리머이다:Block or sequential copolymers are polymers of the form:
-AAAAAABBBBBBAAAAAABBBBBBB- 또는 -AAAAAABBBBBBAAAAAABBBBBBB- or
-AAAAAABBBBBBCCCCCCAAAAAABBBBBB--AAAAAABBBBBBCCCCCCAAAAAABBBBBB-
랜덤 코폴리머는 하기 형태의 폴리머이다:Random copolymers are polymers of the form:
-AABABBAAABABB--AABABBAAABABB-
2순차코폴리머는 하기 형태의 폴리머이다: -(A)n-(B)t-Secondary copolymers are polymers of the form:-(A) n- (B) t-
3순차코폴리머는 하기 형태의 폴리머이다: -(A)m-(B)n-(A)t-Tertiary copolymers are polymers of the form:-(A) m- (B) n- (A) t-
스타형 코폴리머(또는 방사상 코폴리머)는 하기 형태의 폴리머이다:Star copolymers (or radial copolymers) are polymers of the form:
A, B 및 C는 상기 정의된 바와 같은 모노머 단위이다.A, B and C are monomeric units as defined above.
본 발명은 또한 폴리머 표면이 시트(sheet), 판(sheet), 직조물(knitted material), 예를 들면, 카테타(catheter), 스트랜드(strand)와 같은 튜브(tube), 못 또는 나사, 공(ball) 형태 또는 인공 기관(prostheses) 또는 외부 또는 안내 렌즈 (intraocular lens)로 사용할 수 있는 기타 형태로 존재하는 것을 특징으로 하는 하기 정의된 방법에 관한 것이다.The invention also provides that the polymer surface may be a sheet, sheet, knitted material, such as a tube, nail or screw, ball, such as a catheter or strand. ) Or other forms that can be used as prostheses or as external or intraocular lenses.
본 발명의 바람직한 일 실시형태에 따르면, 본 발명은 리티큘레이션(reticulation) 단계를 포함하지 않는 것을 특징으로 한다.According to one preferred embodiment of the invention, the invention is characterized in that it does not comprise a reticulation step.
본 발명은 또한 HO·하이드록실라디칼을 반응시키는 단계가 약 5분 내지 5시간 실행되는 것을 특징으로 하는 상기 정의된 방법에 관한 것이다.The invention also relates to the process as defined above, wherein the step of reacting the HO hydroxyl radicals is carried out in about 5 minutes to 5 hours.
본 발명은 또한 폴리머 표면에 결합된 하이드록실기상에 후속하는 기능화 단계를 포함하는 것을 특징으로 하는 상기 정의된 방법에 관한 것이다.The present invention also relates to the method as defined above, comprising the subsequent functionalization step on the hydroxyl group bound to the polymer surface.
후속하는 기능화 반응은 예를 들어, 카보실산과의 반응에 의한 에스테르형성, 다른 알콜과의 윌리암슨 반응에 의한 에테르 형성, 할라이드산 또는 PCl5과의 반응에 의한 할라이드 형성, 미쯔노브반응(Mitsunobu reaction)에 의한 N-알킬아미드의 형성, 티올과의 반응에 의한 설파이드의 형성을 들 수 있다.Subsequent functionalization reactions include, for example, ester formation by reaction with carbolic acid, ether formation by Williamson reaction with other alcohols, halide formation by reaction with halide acid or PCl 5 , Mitsunobu reaction Formation of N-alkylamides and the formation of sulfides by reaction with thiols.
일반적으로, 후-기능화는 본 기술분야의 당업자로 하여금 예를 들면 생물의학 도메인에서 단백의 흡착 또는 비흡착, 약학적 물질, 항생제의 결합과 같은 목적하는 분야에서의 응용을 위하여 선택한 유기 기능기를 표면에 부착할 수 있게 한다. In general, post-functionalization allows the person skilled in the art to surface organic functional groups selected for application in the desired field, such as, for example, adsorption or non-adsorption of proteins in the biomedical domain, binding of pharmaceutical substances, antibiotics, etc. To be attached.
후속하는 기능화 반응은 예를 들면 생물학적으로 활성인 분자(예를 들면, 효소) 또는 약학적 성질을 갖는 물질 등의 결합에 의해 표면에 특정 성질을 부여할 수 있도록 한다. 이는 표면에 0H기를 직접 원하는 분자와 결합시키거나, 중간 결합에서 중간체를 통해 수행된다. 알콜 기능기는 에스테르 형성(무수물, 산클로라이드 또는 산과의 반응에 의해), 아미드 형성(이소시아네이트와의 반응에 의해) 또는 에테르 형성(알킬 할라이드와의 반응에 의해)에 의해 연결할 수 있다.Subsequent functionalization reactions make it possible to impart specific properties to the surface, for example by binding of biologically active molecules (eg, enzymes) or substances with pharmaceutical properties. This is done via the intermediate at the intermediate bond or with the 0H group directly on the surface. Alcohol functional groups can be linked by ester formation (by reaction with anhydrides, acid chlorides or acids), amide formation (by reaction with isocyanates) or ether formation (by reaction with alkyl halides).
본 발명은 또한 물방울과 수득되는 하이드록실화 표면과의 사이에 측정되는 접촉각이 물방울과 비-하이드록실화 표면과의 사이에서 측정되는 접촉각에 비하여 5°이상, 특히 10°이상 감소하는 것을 특징으로 하는 하기 정의된 바에 의한 하이드록실화 방법에 관한 것이다.The present invention is also characterized in that the contact angle measured between the water droplet and the obtained hydroxylated surface is reduced by at least 5 °, in particular at least 10 ° compared to the contact angle measured between the droplet and the non-hydroxylated surface. To a hydroxylation method as defined below.
접촉각은 주사기를 사용하여 물방울을 폴리머 표면에 떨어뜨리고, 이후 현미경을 사용하여 폴리머와의 접촉점에 의해 폴리머 표면과 방울의 접선간에 형성되는 각을 측정함으로써 측정한다. The contact angle is measured by dropping the droplet onto the polymer surface using a syringe and then measuring the angle formed between the polymer surface and the tangent of the droplet by the point of contact with the polymer using a microscope.
표면이 친수성일수록 측정되는 접촉각은 작아지고, 표면이 소수성일수록 측정되는 접촉각은 커진다.The more hydrophilic the surface, the smaller the measured contact angle, and the more hydrophobic the surface, the larger the measured contact angle.
본 발명은 또한 수득된 하이드록실화, 알콕시화, 또는 옥시카보닐화 표면이 시간에 대해 안정적이고, 특히 하기 시험에 따라 많은 주(weeks) 동안 안정한 것을 특징으로 하는 상기 정의된 방법에 관한 것이다.The invention also relates to the process as defined above, wherein the hydroxylated, alkoxylated, or oxycarbonylated surface obtained is stable over time, especially for many weeks according to the following test.
10분 동안 또는 120분 동안 전기펜톤에 의해 개질되고 이후 트리플루오로아세틸화된 PET 및 PEEK 샘플의 적외선 스팩트럼을 74일 후 다시 기록하였다. 스펙트럼 차이를 기록한 결과(t=0 및 t=74일), 어떠한 유의성 있는 차이 특히 트리플루오로아세틸기(trifluoroacetyl group)에 해당하는 특징적인 밴드의 소실이 나타나지 않았다.Infrared spectra of PET and PEEK samples modified with electropentone for 10 minutes or 120 minutes and then trifluoroacetylated were recorded again after 74 days. As a result of recording the spectral differences (t = 0 and t = 74 days), there was no significant difference in the disappearance of the characteristic bands corresponding to the trifluoroacetyl group.
본 발명은 또한 상기 정의된 바와 같은 발명의 방법을 사용하여 수득된 하이드록실화, 알콕시화 또는 옥시카보닐화 표면에 관한 것이다.The present invention also relates to hydroxylated, alkoxylated or oxycarbonylated surfaces obtained using the inventive process as defined above.
하기 실험부분에 보고된 접촉각의 측정으로부터 알 수 있는 바와 같이, 처리된 표면은 매우 친수성(하이드록실화의 경우)으로 되었으며, 결과적으로 더욱 생체-적합성으로 되었다.As can be seen from the measurement of the contact angle reported in the experimental section below, the treated surface became very hydrophilic (in the case of hydroxylation), resulting in more bio-compatibility.
폴리머와 OH기와의 결합은 공유 결합이었으며, 그 에너지는 390(CH3OH) 내지 470kJ/mol(C6H5OH)의 범위 내이었다.The bond between the polymer and the OH group was a covalent bond and its energy was in the range of 390 (CH 3 OH) to 470 kJ / mol (C 6 H 5 OH).
I-일렉트로-펜톤 반응I-electro-Fenton reaction
폴리에틸렌테레프탈레이트Polyethylene terephthalate (( PETPET ), ), 폴리에테르에테르케톤Polyether ether ketone (( PEEKPEEK ) 및 ) And 아크릴로니트릴Acrylonitrile -부타디엔-스티렌(Butadiene-styrene ABSABS )의 )of 하이드록실화Hydroxylation
기질 - 직조된 PET 및 ES304045 시트 Substrate -Woven PET and ES304045 Sheet
- PEEK(굿펠로우 EK 113000 시트) PEEK (Goodfellow EK 113000 sheet)
- ABS 판(Goodfellow, AB3030090)[아크릴로니트릴 과 스티렌의 공중합에 의해 수득된 스티렌 상(SAN)에 엘라스토머 상(부타디엔)을 분산함으로써 수득함) ABS plate (Goodfellow, AB3030090) (obtained by dispersing an elastomeric phase (butadiene) in a styrene phase (SAN) obtained by copolymerization of acrylonitrile and styrene)
전기화학적 장치:Electrochemical Device:
비분리 콤파트먼트셀Non-isolated compartment cell
애노드: 카본Anode: carbon
캐소드: 카본 펠트 (약 10 cm2)Cathode: carbon felt (approx. 10 cm 2 )
폴리머 시트나 직조물은 시트에 단단하게 고정시키거나 또는 캐소드로 작용하는 두개의 카본 펠트 시트 사이에 위치시켰다.The polymer sheet or woven fabric was placed between two carbon felt sheets that would either hold the sheet tightly or act as a cathode.
용매 0.1M H2SO4는 수산화나트륨으로 pH 3으로 조정하였다.Solvent 0.1MH 2 SO 4 was adjusted to pH 3 with sodium hydroxide.
촉매제 0.5 mM Fe2 + (FeSO4. 7H2O)Catalyst 0.5 mM Fe 2 + (FeSO 4 . 7H 2 O)
연속 에어버블링(Air bubbling)Continuous air bubbling
정전류법(Galvanostatic method): 일정 전류: 10 mA 또는 실험에 따라 5 mA Constant-current method (Galvanostatic method): 5 mA or 10 mA, depending on the experiment: a constant current
정전위법(Potentiostatic method): 일정 전위 E = -0.6V/SCE Electrostatic illegal (Potentiostatic method): a constant potential E = -0.6V / SCE
A) PET 의 하이드록실화 A) hydroxylation of PET
시트의 Of sheet 하이드록실화Hydroxylation
a) 정전류법에 의하여 i= 5 mA, 2 시간:a) i = 5 mA, 2 hours by constant current method:
상대-전극은 기준에 대하여 단락되었다. The counter-electrode is shorted with respect to the reference.
캐소드 전위는 실험 초기 약 -0.6V/SCE에서 실험이 끝날 즈음 약 -2V/SCE로 증가되었으며, 이 전위에서 프로톤이 환원되어 산소의 환원 효율이 감소되었다. The cathode potential was increased from about -0.6V / SCE at the beginning of the experiment to about -2V / SCE at the end of the experiment, and proton was reduced at this potential to reduce the reduction efficiency of oxygen.
샘플은 조심스럽게 소니케이션하면서 10분간 증류수로, 이후 아세토니트릴 (분석용)내에서 10분간 세척하고, 밤새 40℃에서 진공하 건조하였다.The sample was washed with distilled water for 10 minutes with gentle sonication, then for 10 minutes in acetonitrile (analytical), and dried under vacuum at 40 ° C. overnight.
b) 정전위법에 의하여, 전류는 약 30에서 10 mA로 감소하였다. 샘플은 전술한 바와 같이 처리하였다.b) By the potentiometry, the current decreased from about 30 to 10 mA. Samples were treated as described above.
IR분석을 위해, 샘플을 에테르(30 mL)내 트리플루오로아세트산무수물(1 mL) 용액으로 처리하고, 아세토니트릴로 세척한 후 밤새 진공하에서 건조하였다. 그 결과를 표 1에 나타내었다.For IR analysis, the samples were treated with a solution of trifluoroacetic anhydride (1 mL) in ether (30 mL), washed with acetonitrile and dried under vacuum overnight. The results are shown in Table 1.
[표 1] 하이드록실화 이후 트리플루오로아세틸화된 PET 시트*의 IR 분석Table 1 IR analysis of trifluoroacetylated PET sheet * after hydroxylation
(CF3CO)2O에 대해서는 약 1813 cm-1에서,
CF3COOH에 대해서는 약 1780cm-1에서 관찰 The C═O band of the PET itself was observed at 1714 cm −1 .
For (CF 3 CO) 2 O at about 1813 cm -1 ,
Observed about CF 3 COOH at about 1780cm -1
기준 : 비-처리된 PET 시트.Criteria: Non-treated PET sheet.
정전류법과 정전위법 실험간에는 유의성 있는 차이가 관찰되지 않았다.No significant difference was observed between the constant current and the electropotential experiments.
물 방울의 접촉각은 약 90 정도 감소되었으며, 방울을 접촉시킨 직후에는 거의 차이가 없었으나, 약 5분 후에는 55°에 도달하고 그 후 감소하였다.The contact angle of the water droplets decreased by about 90, and there was little difference immediately after contacting the droplets, but after about 5 minutes it reached 55 ° and then decreased.
ToF-SIMS 분석 결과로부터 표면의 트리플루오로메틸화를 확인할 수 있었으며, 그 단편을 하기 표 2에 기재하였다.From the results of the ToF-SIMS analysis, it was possible to confirm trifluoromethylation of the surface, and fragments thereof are shown in Table 2 below.
-OH + CF3(C=O)O(O=C)CF3 ⇒ -O(C=O)CF3 -OH + CF 3 (C = O) O (O = C) CF 3 ⇒ -O (C = O) CF 3
[표 2] 하이드록실화 이후 트리플루오로아세틸화된 PET 시트의 ToF-SIMS 분 석TABLE 2 ToF-SIMS analysis of trifluoroacetylated PET sheet after hydroxylation
또는 이성질체{C (= O) OCH 2 CH (OC (= O) CF 3 ) C (= O) H} -
Or isomer
직조물의Weave 하이드록실화Hydroxylation
전기분해 1 시간. 정전류법: i = 10mA1 hour electrolysis. Constant current method: i = 10 mA
IR 분석 : 비처리된 샘플에 비교시, OH 신축 진동에 기인되는 3380 cm-1 밴드가 관찰되었다. IR analysis: Compared to the untreated sample, a 3380 cm −1 band was observed due to OH stretching vibrations.
접촉각: 직조물상에서, 비처리 샘플의 경우 접촉각은 약 90°이었으나, 반면 처리된 샘플상에서는 물이 원단을 완전히 통과하였다. Contact angle: On the woven fabric, the contact angle was about 90 [deg.] For the untreated sample, while water passed completely through the fabric on the treated sample.
하이드록실화된 표면의 ToF-SIMS 분석 결과, m/z = 138에서 피크를 나타내었으며, 이는 하이드록실화된 폴리머의 단편에 해당하는 이온 [0-(C=O)C6H4OH]- (동일한 프로톤화된 종이 양이온에서도 보였다)에서 기인되는 것이다.ToF-SIMS analysis results of a hydroxyl misfire surface, m / z = exhibited a peak at 138, which is an ion corresponding to a fragment of a hydroxylated polymer [0- (C = O) C 6 H 4 OH] - (The same protonated species were also seen in the cation).
B) B) PEEKPEEK 의 of 하이드록실화Hydroxylation
굿펠로우시트(Good Fellow Sheet ( GoodfellowGoodfellow sheetsheet ))
정전류법 및 정전위법에 의하여 전술한 바와 동일한 조건하에서 처리하였다. ToF-SIMS 분석 결과, 비처리된 기준과 달리, 식 HOC6H4C(=O)C6H3(OH)2 에 기인되는 m/z= 231에서의 피크(음이온으로서); m/z = 97, 79 (97-H2O) 및 63 (79-O)에서 피크가 관찰되었다.Treatment was carried out under the same conditions as described above by the constant current method and the electropotential method. ToF-SIMS analysis showed that, as an anion, the peak at m / z = 231 due to the formula HOC 6 H 4 C (= 0) C 6 H 3 (OH) 2 , as opposed to untreated criteria; Peaks were observed at m / z = 97, 79 (97-H 2 O) and 63 (79-O).
트리플루오로아세틸화 후, 두 샘플을 IR로 분석하였다. After trifluoroacetylation, both samples were analyzed by IR.
[표 3] 하이드록실화 그 후 트리플루오로아세틸화된 PEEK 시트*의 IR 분석TABLE 3 IR analysis of trifluoroacetylated PEEK sheet * after hydroxylation
(벤조페논단위)C = O bands of PEEK itself is 1653 cm - it was observed in the 1
(Benzophenone unit)
기준 : 비-처리된 PEEK시트.Criteria: Non-treated PEEK sheet.
[표 4] 굿펠로우 PEEK 시트의 ToF-SIMS 분석Table 4 ToF-SIMS Analysis of Goodfellow PEEK Sheet
정전류법과 정전위법 실험간에는 유의성 있는 차이가 관찰되지 않았다.No significant difference was observed between the constant current and the electropotential experiments.
PEEK 상에서의 물방울의 접촉각은 약 87°였으며, 정전위 전기펜톤 반응에 의하여 처리한 후 65°로 감소되었다.The contact angle of the droplets on the PEEK was about 87 ° and was reduced to 65 ° after treatment by the potentioelectric Fenton reaction.
C) C) ABSABS 의 of 하이드록실화Hydroxylation
정전류법 및 정전위법에 의하여 전술한 바와 동일한 조건하에서 처리하였다. Treatment was carried out under the same conditions as described above by the constant current method and the electropotential method.
하이드록실화된 표면의 IR 스펙트럼이 기록되었다.The IR spectrum of the hydroxylated surface was recorded.
[표 5] 처리후 ABS의 IR 스펙트럼[Table 5] IR spectrum of ABS after treatment
*비처리된 기준을 차감한 후, 샘플은 2일간 40℃에서 진공하 건조하여, OH 밴드가 잔여하는 습도에서 기인되지 않도록 하였다. After subtracting the untreated criteria, the samples were dried under vacuum at 40 ° C. for 2 days to ensure that the OH band was not due to the residual humidity.
샘플을 전술한 바와 같이 트리플루오로아세틸화하였다. 하이드록실화되지 않은 샘플을 트리플루오로아세틸화 처리하여 기준을 수득하였다.Samples were trifluoroacetylated as described above. Trihydroxyacetylation of the non-hydroxylated samples gave a reference.
[표 6] 하이드록실화 이후 트리플루오로아세틸화된 ABS 시트*의 IR 분석Table 6 IR analysis of trifluoroacetylated ABS sheet * after hydroxylation
CF3COOH에 대해서는 약 1780 cm- 1 에서 관찰Observed about (CF 3 CO) 2 O at about 1813 cm - 1
Observed about 1780 cm - 1 for CF 3 COOH
1160 쇼울더링1245 shouldering
1160 Shouldering
기준 : 비-하이드록실화된 ABS sheet를 트리플루오로아세틸화 처리Criterion: Trifluoroacetylation of non-hydroxylated ABS sheet
[표 7] 하이드록실화 이후 트리플루오로아세틸화된 ABS 시트*의 ToF-SIMS 분석TABLE 7 ToF-SIMS analysis of trifluoroacetylated ABS sheet * after hydroxylation
ABS 상에서의 물방울의 접촉각은 69°였으며, 정전위 전기펜톤 반응에 의하여 처리한 후 37°로 감소되었다.The contact angle of the water droplets on the ABS was 69 ° and decreased to 37 ° after treatment by the electropotential electro-Fenton reaction.
폴리머Polymer 이식에 대한 반응 시간의 영향 Effect of Response Time on Transplantation
각각 PET 또는 PEEK 샘플을 포함하는 카본 펠트 "엔벨로프"를 전기펜톤 용액에 넣었다. 전기펜톤 반응은 전술한 바와 같은 정전위 모드로 실행되었다. 엔벨로프를 10분, 30분, 60분, 90분, 120분 후 용액에서 회수하고; 폴리머 샘플을 증류수를 포함하는 세척 병을 사용하여 증류수로 15분간 두번 세척하고, 소니케이션하 분석용 아세토니트릴로 15분간 한 번 세척하고, 40℃에서 2일간 진공하에서 건조하였다(기준과 동일한 시간에). IR 스펙트럼을 기록하고 기준에서 차감한 후 분석하였다.Carbon felt “envelopes” each containing a PET or PEEK sample were placed in an electrofenton solution. The electrofenton reaction was carried out in the potential potential mode as described above. The envelope was recovered from the solution after 10, 30, 60, 90, 120 minutes; The polymer sample was washed twice with distilled water for 15 minutes using a wash bottle containing distilled water, washed once with 15% analytical acetonitrile under sonication and dried under vacuum at 40 ° C. for 2 days (at the same time as the reference). ). IR spectra were recorded and subtracted from baseline and analyzed.
PETPET
PET 자체의 1714 cm-1 (매우 미약)에서의 밴드를 분석한 결과, 이는 30분 후 실질적으로 사라졌으며, 반면 1131 cm-1 (강함)의 밴드는 반응 60분 후 실질적으로 소실되었다.Analyzing the band at 1714 cm −1 (very weak) of the PET itself, it disappeared substantially after 30 minutes, while the band of 1131 cm −1 (strong) was substantially lost after 60 minutes of reaction.
PEEKPEEK
상기 폴리머와 달리, CF3 밴드 1217 및 1186 cm-1 (C=O 밴드 1788 cm-1 는 너무 미약하여 분석할 수 없었다)에서는 실질적인 변경이 관찰되지 않았다. Unlike the polymer, no substantial alteration was observed in the CF 3 bands 1217 and 1186 cm -1 (the C = O band 1788 cm -1 was too weak to be analyzed).
PET의 하이드록실화 반응은 10 내지 30분에서 최대에 도달하는 반면, PEEK 하이드록실화는 반응 10분 후 일정하게 유지되는 것으로 보였다. 따라서 10분의 반응 시간은 최대 하이드록실화에 도달하기에 충분하였으며, 이 시간을 넘어선 추가 반응은 PET의 분해를 초래하였다.The hydroxylation reaction of PET reached its maximum at 10-30 minutes, while the PEEK hydroxylation appeared to remain constant after 10 minutes of reaction. Thus, a reaction time of 10 minutes was sufficient to reach maximum hydroxylation, and further reactions beyond this resulted in the degradation of PET.
시간에 따른 이식 안정성Transplant Stability Over Time
10분 또는 120분 동안 전기펜톤 반응에 의하여 개질되고 트리플루오로아세틸화된 PET 및 PEEK 샘플에 대하여 74일 후 적외선 스펙트럼을 기록하였다. 스펙트럼의 차이를 분석한 결과(t=0 및 t=74일), 특별한 차이 및 트리플루오로아세틸기의 특징적인 밴드의 소실이 관찰되지 않았다. Infrared spectra were recorded after 74 days for PET and PEEK samples modified and trifluoroacetylated by an electro-Fenton reaction for 10 or 120 minutes. As a result of analyzing the differences in the spectra (t = 0 and t = 74 days), no particular differences and loss of characteristic bands of the trifluoroacetyl group were observed.
II - 광펜톤 반응II-photophentone reaction
폴리에틸렌테레프탈레이트(PET) 및 폴리에테르에테르케톤(PEEK)의 하이드록 실화Hydroxylation of Polyethylene Terephthalate (PET) and Polyetheretherketone (PEEK)
기질 PET 및 시트 (DSM) Substrate PET and Sheet (DSM)
PEEK(굿펠로우 시트) PEEK (Good Fellow Seat)
실시예Example 1 One
순환 펌프, 항온이중자켓을 장착하고, 반응기 중앙에 석영 튜버내 저압 수은 램프를 위치시킨 2 L 유리 반응조를 2 L의 1 mM HCl 수용액, 1 g의 염화제2철 및 2 mL의 과산화수소로 채웠다. 폴리머 샘플을 용액내 분산시켰다. 펌프 및 조사를 시작하고; 2시간 30분 후 조사를 중단하였다. 샘플을 소니케이션하면서 증류수, 이후 아세톤으로 15분간 세척하고, 밤새 40℃에서 진공하 건조하였다.A 2 L glass reactor, equipped with a circulation pump, a constant temperature double jacket and a low pressure mercury lamp in a quartz tube at the center of the reactor, was charged with 2 μL of a 1 Mm HCl aqueous solution, 1 g of ferric chloride and 2 mL mL of hydrogen peroxide. The polymer sample was dispersed in solution. Start pumping and irradiation; The irradiation was stopped after 2 hours and 30 minutes. The sample was washed with distilled water, followed by acetone for 15 minutes while sonicating, and dried under vacuum at 40 ° C. overnight.
물과의 접촉각 계산은 처리 전 및 후에 수행하였다.Contact angle calculations with water were performed before and after the treatment.
[표 8] 광펜톤에 의해 처리된 폴리머 샘플의 접촉각TABLE 8 Contact angles of polymer samples treated with light pentones
62 (5'후)88 a)
62 (after 5 ')
a) 물방울을 떨어뜨린 직후a) immediately after dropping
b) 방울 크기에는 주목할만한 감소가 없음b) no noticeable decrease in droplet size
이후 샘플을 트리플루오로아세트산무수물(10 mL의 에테르내 0.4 mL)로 처리하고 IR 분석하였다. 세 샘플에 대해, 트리플루오로아세트산 및 트리플루오로산무 수물의 스펙트럼과 비교하여 CF3 기에 기인되는 1206-1254 cm-1 및 1165-1185 cm-1 위치의 밴드가 명확히 관찰되었다. 카보닐기(C=O)CF3 에 해당하는 진동이 PEEK상에서 관찰되었다. 이들 스펙트럼들로부터 폴리머 표면의 개질을 명확히 확인할 수 있었다.The sample was then treated with trifluoroacetic anhydride (0.4 mL in 10 mL ether) and IR analyzed. For the three samples, the bands at positions 1206-1254 cm −1 and 1165-1185 cm −1 due to CF 3 groups were clearly observed compared to the spectra of trifluoroacetic acid and trifluoroacid anhydride. Vibration corresponding to the carbonyl group (C═O) CF 3 was observed on PEEK. From these spectra the modification of the polymer surface can be clearly seen.
[표 9] 트리플루오로아세틸화 샘플의 IR 스펙트럼Table 9 IR Spectrum of Trifluoroacetylated Samples
1165 m1254 s
1165 m
CF3 ((CF3CO)2O 에 대해서는 1195 및 CF3COOH에 대해서는 1177)CF 3 (1248 for (CF3CO) 2 O and 1240 for CF 3 COOH)
CF 3 (1195 for (CF3CO) 2 O and 1177 for CF 3 COOH)
1215 m
1185 m≒ 800 vw
1215 m
1185 m
CF3 ((CF3CO)2O 에 대해서는 1248 및
CF3COOH에 대해서는 1240)
CF3 ((CF3CO)2O에 대해서는 1195 및
CF3COOH에 대해서는 1177)C = O (about 1790 cm -1 for CF 3 COOH)
1248 for CF 3 ((CF3CO) 2 O and
1240 for CF 3 COOH)
1195 for CF 3 ((CF3CO) 2 O and
1177 for CF 3 COOH)
a) 폴리머 스펙트럼 그 자체는 차감 후a) the polymer spectrum itself is subtracted
[표 10] 트리플루오로아세틸화 샘플의 ToF-SIMS 스펙트럼TABLE 10 ToF-SIMS Spectrum of Trifluoroacetylated Samples
PET
PEEK a
접촉각 변경, IR 스펙트럼 및 ToF-SIMS 스펙트럼으로부터 아세트산무수물 처리후 OCF3기에 의한 폴리머 이식, 즉 표면 하이드록실화를 명백히 확인할 수 있었다.From the contact angle change, the IR spectrum and the ToF-SIMS spectrum, the polymer implantation by the OCF 3 group after the acetic anhydride treatment, namely surface hydroxylation, was clearly confirmed.
라우릴Lauryl 퍼옥사이드를Peroxide 사용한, Used, 펜톤Fenton 동족 반응 Cognate reaction
PET 샘플을 전술한 바와 같이 준비하여, 수산화나트륨으로 pH 3으로 조정하고 400 mg의 라우릴 퍼옥사이드 (CH3(CH2)10C(=O)OOC(=O)(CH2)10CH3) (포화용액) 및 55 mg의 FeSO4, 5H2O (0.5 mM)을 첨가한 360 mL의 0.1N H2SO4용액에 넣었다. 카본 펠트내 엔벨로프된 샘플을 캐소드로서 사용하고, 전위를 -0.6 V/SCE로 2시간 동안 고정한 후, 담수로 세척하고, 소니케이션하에서 10분간 증류수로 두번, 소니케이션하에서 10분간 아세톤으로 한 번 세척한 후, 진공하에서 건조하였다. 라우릴 퍼옥사이드 용해성을 증가시키기 위하여, 50% 아세토니트릴 용액을 상기 용액내 첨가하였 으며, 이는 결과에 특별한 영향을 미치지 않았다(ToF-SIMS에서 상대적 피크 강도 밖). PET 샘플을 ToF-SIMS로 분석한 결과, PET는 개질된 표면을 나타내었다.A PET sample was prepared as described above, adjusted to pH 3 with sodium hydroxide and 400 mg of lauryl peroxide (CH 3 (CH 2 ) 10 C (= 0) OOC (= 0) (CH 2 ) 10 CH 3 ) (Saturated solution) and 55 mg of FeSO 4 , 5H 2 O (0.5 mM) were added to 360 mL of 0.1NH 2 SO 4 solution. The enveloped sample in carbon felt was used as cathode, the potential was fixed at -0.6 V / SCE for 2 hours, then washed with fresh water, twice with distilled water for 10 minutes under sonication, and once with acetone for 10 minutes under sonication. It was then dried under vacuum. To increase the lauryl peroxide solubility, a 50% acetonitrile solution was added in the solution, which had no particular effect on the results (out of relative peak intensity in ToF-SIMS). PET samples were analyzed by ToF-SIMS and the PET showed a modified surface.
[표 11] 펜톤 반응 조건하에서 라우릴 퍼옥사이드로 처리한 PET 샘플의 ToF-SIMS 분석 Table 11 ToF-SIMS analysis of PET samples treated with lauryl peroxide under Fenton reaction conditions
결론conclusion
광화학 또는 전기화학에 의한 펜톤 반응에 의하여 폴리머 표면을 하이드록실화하는 것을 많은 실시예를 들어 기술하였다. 반응은 매우 효율적인 것으로 증명되었으며, 특히 PEEK와 같이 매우 활동성이 낮은 폴리머에 대해서도 매우 효율적이었다. 본 반응은 폴리머 기능에만 특정되는 것이 아니며, 어떠한 폴리머에도 적용될 수 있다. 펜톤 반응 조건하에서 PET에 대한 라우릴 퍼옥사이드를 사용한 반응도 증명되었다. The hydroxylation of polymer surfaces by Fenton reaction by photochemistry or electrochemistry has been described for many examples. The reaction proved to be very efficient, especially for very inactive polymers such as PEEK. The reaction is not specific to polymer function, but may be applied to any polymer. The reaction with lauryl peroxide on PET under Fenton reaction conditions has also been demonstrated.
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